Curable liquid resin composition

ABSTRACT

A curable liquid resin composition containing 100 parts by weight of the following (meth)acrylic liquid resin (A) and 1 to 1,000 parts by weight of a (meth)acrylic monomer (B) having an unsaturated double bond in its molecule and having a number average molecular weight of 1,000 or less, the (meth)acrylic liquid resin (A) being a liquid resin which is obtained by polymerizing monomers containing an alkyl (meth)acrylate monomer (a-1-1) of the formula (1), 
     
         CH.sub.2 C(R.sup.1)COO--R.sup.2                            (1) 
    
     wherein R 1  is a hydrogen atom or CH 3  and R 2  is an alkyl group, 
     and/or an alkylene glycol (meth)acrylate monomer (a-1-2) of the formula (2), 
     
         CH.sub.2 ═C(R.sup.1)COO(C.sub.n H.sub.2n O).sub.m R.sup.3(2) 
    
     wherein R 1  is a hydrogen atom or CH 3 , R 3  is an alkyl group or a phenyl group, n is an integer of 1 to 3, and m is an integer of 3 to 25, and other polymerizable vinyl monomer (a-2), an average of molecular weights of all the monomers being 100 to 1,500, the liquid resin having a number average molecular weight of 10,000 to 200,000 and a viscosity of 1 to 10,000 poise (measured at 50° C.), or a modified product of the above liquid resin, the curable liquid resin composition can form a film as a film-forming material or as a resin for an adhesive without using a solvent and give a cured film.

TECHNICAL FIELD

The present invention relates to a liquid resin composition which canform a film and give a cured film without using a solvent, as a resinfor a film-forming material such as an ink or for an adhesive. Further,the present invention relates to a liquid resin composition containingan acrylic liquid resin and a (meth)acrylic monomer, which can be usedas a vehicle for a printing ink, a coating composition, an adhesive, orthe like, used as a radiation-curable resin composition.

TECHNICAL BACKGROUND

Conventionally, a coating composition, an adhesive, an adhesive mass, anink, a filler and a molding material contain resin solutions containingorganic solvents. These resin solutions dissipate large amounts oforganic solvents in the steps of coating and charging and in the stepsof curing and drying. With increasing concerns about global environmentsand working environments, restrictions have come to be imposed on theuse of the above resin solutions. one of methods for overcoming theabove problem uses an aqueous solution of a resin, a powder or ahot-melt material. However, an aqueous solution of a resin contains anorganic solvent to some extent for improving coating properties, and itcan hardly be said that the aqueous solution of a resin is free of anodor in a working environment. Further, not only it is required toincinerate a discharged organic solvent, but also the disposal of itseffluent requires an investment. In a coating or charging plant havinglarge-scale equipment for the treatment of discharged gas, the releaseof an organic solvent to atmosphere can be prevented, while asmall-scale plant having no such equipment has a problem that aneffluent containing an organic solvent cannot be treated. The coating orcharging of a powder or a holt melt requires equipment and a methodwhich are quite different from conventional ones, and it is thereforerequired to introduce new equipment. For overcoming the above problems,attempts are being made to form a high-solid resin solution and toimprove an aqueous solution of a resin, and it is considered that theamount of a resin solution remarkably tends to decrease owing to theabove efforts. As an essential solution, however, it is strongly desiredto develop a solventless liquid resin which is free from problemsconcerning pollution, hygienic safety, ignition, explosion, etc., whichcan be widely applied and which can be easily applied. Further, thesolventless liquid resin is required to form a cured film or a shapedarticle by means of a conventional drying appratus.

Further, concerning a conventional radiation-curable resin composition,its viscosity is controlled by incorporating a large amount of acomponent having a low molecular weights However, the incorporation of acomponent having a low molecular weight is not desirable in view of aworking environment since it causes problems of odor, etc. There arefurther another problems that a volume shrinkage takes place at a curingtime and a cured film becomes fragile. For improving the curing-causedshrinkage ratio, attempts have been made to use a monomer componenthaving a relatively high molecular weight or to add a component having ahigh molecular weight. However, since the latter component is in thestate a solid, the amount of the component that can be added is limitedin order to keep the viscosity of the composition in a proper range.Further, there are problems caused by a large content of a compoundhaving a low molecular weight such as a problem on an odor caused by aresidual monomer, and these problems limit the radiation-curable resincomposition in use.

JP-A-57-171 discloses a technique concerning a solventless resincomposition. This technique uses a liquid resin containing an acrylicmonomer, while the technique is desired to be further improved since anobtained resin is an oligomer. Further, in view of physical properties,it is known that it is difficult to control the physical properties of acured film obtained from a coating composition containing a resin whichis in an oligomer region (MUROI Soichi, "Lectures in Society of Adhesionand coating Studies in 1992", Summary Prints of Lectures, page 4, 1993),and it is desired to increase a molecular weight while maintaining a lowviscosity.

In reactions for curing resins with various kinds of radiation as atrigger, a radical-based crosslinking reaction and a cation-basedcrosslinking reaction are well known. A composition using aradical-based crosslinking reaction causes an extreme curing shrinkage.On the other hand, a cation-curable composition containing an alicyclicepoxy compound is improved in curing shrinkage to some extent. However,in particular, when an alicyclic epoxy resin having a low molecularweight and having a low viscosity and a high dilution effect is used, avolume change occurs at a curing time. JP-A-2-289611 discloses aninvention of an acrylic resin having an alicyclic epoxy group. It can besaid that the above invention further moderates a volume change at acuring time. In this technique, however, the acrylic resin contains alarge amount of an organic solvent since it is synthesized by a solutionmethod, and it is required to remove the solvent by some method in orderto obtain a solventless resin composition. Further, since a cationicpolymerization initiator is used as an essential component, it can besaid that there are problems on the safety and hygiene which remain tosolve.

Not only for the reaction of an alicyclic epoxy group, but also for thecuring reaction with ultraviolet light, it is required to add a largeamount of an initiator. The initiator and a sensitizer migrate out of acured film, and this migration phenomenon has been a problem in view ofsafety and hygiene. When a high-energy radiation such as an electronbeam or y ray is used as a trigger, a radical curable compositionrequires no catalyst. However, it is pointed out by J. V. Crivello et althat the cationic reaction of an alicyclic epoxy resin essentiallyrequires an initiator, a particularly harmful antimony-containingcatalyst, and the cationic reaction of an alicyclic epoxy resin deviatesfrom the advantage of an electron-beam-curable composition that noinitiator is required.

The present inventors have made diligent studies of a correlationbetween the structure and the viscosity of various resin compositions,and as a result, have found a solventless, radiation-curable liquidresin composition which contains a large amount of a component having ahigh molecular weight but has a viscosity sufficient forfilm-formability by a conventional film-forming method, and which can becured at a high rate by a conventional curing method using radiation asa trigger. Further, by introducing an alicyclic epoxy group for a sidechain component of a liquid resin having a high molecular weight, therecan be obtained a radiation-curable liquid resin composition containingan alicyclic-epoxy-containing resin having a high molecular weight andcontaining neither an alicyclic epoxy compound having a low molecularweight nor a solvent.

It is an object of the present invention to provide a solventlesscurable liquid resin composition containing a liquid polymer having ahigh molecular weight and containing no solvent. The above curableliquid resin composition serves to decrease the amount ratio of acompound having a low molecular weight, which compound causes a problemwith regard to safety and physical properties, and it serves to improveworking environments. Further, it is another object of the presentinvention to provide a curable liquid resin composition capable offorming a film by a conventional coating method using a roll coater or aknife coater or a conventional printing method such as an offsetprinting method, a gravure printing method, a letterpress printingmethod or a screen printing method. It is further another object of thepresent invention to provide a radiation-curable liquid resincomposition which can be cured by the irradiation with a conventionalradiation such as ultraviolet light, electron beam or γ ray, or whichcan be cured in the absence of a catalyst and an initiator by theirradiation with electron beam or γ ray in particular.

DISCLOSURE OF THE INVENTION

According to the present invention, there is provided a curable liquidresin composition containing 100 parts by weight of the following(meth)acrylic liquid resin (A) and 1 to 1,000 parts by weight of a(meth)acrylic monomer (B) having an unsaturated double bond in itsmolecule and having a number average molecular weight of 1,000 or less,

the (meth)acrylic liquid resin (A) being a liquid resin which isobtained by polymerizing monomers containing

10 to 100% by weight of an alkyl (ineth)acrylate monomer (a-1-1) of theformula (1),

    CH.sub.2 ═C(R.sup.1)COO--R.sup.2                       (1)

wherein R¹ is a hydrogen atom or CH₃ and R² is an alkyl group having 4to 22 carbon atoms,

and/or an alkylene glycol (meth)acrylate monomer (a-1-2) of the formula(2),

    CH.sub.2 ═C(R.sup.1)COO(C.sub.n H.sub.2n,O).sub.m R.sup.3(2)

wherein R¹ is a hydrogen atom or CH₃, R³ is an alkyl group having 1 to 5carbon atoms or a phenyl group, n is an integer of 1 to 3, and m is aninteger of 3 to 25, and

0 to 90% by weight of other polymerizable vinyl monomer (a-2), anaverage of molecular weights of all the monomers being 100 to 1,500,

the liquid resin having a number average molecular weight of 10,000 to200,000 and a viscosity of 1 to 10,000 poise (50° C.), or the(meth)acrylic liquid resin (A) being a modified product of the aboveliquid resin.

Further, in the above curable liquid resin composition providedaccording to the present invention, the (meth)acrylic liquid resin (A)contains 1 to 50% by weight of a vinyl monomer (a-2-1) having afunctional group inert to radiation as a polymerizable vinyl monomer(a-2).

Further, in the above curable liquid resin composition providedaccording to the present invention, the vinyl monomer (a-2-1) is atleast one monomer selected from the group consisting of alkyl(meth)acrylate whose alkyl group has 3 carbon atoms or less, an alkyleneglycol (meth)acrylate monomer of the formula (3),

    CH.sub.2 ═C(R.sup.1)COO(C.sub.n H.sub.2n,O).sub.m R.sup.3(3)

wherein R¹ is a hydrogen atom or CH₃, R³ is an alkyl group having 1 to 5carbon atoms or a phenyl group, n is an integer of 1 to 4, and m is aninteger of 2 or less,

styrene and vinyl toluene.

Further, in the above curable liquid resin composition providedaccording to the present invention, the vinyl monomer (a-2-1) is atleast one monomer selected from the group consisting of acarboxyl-group-containing vinyl monomer, a hydroxyl-group-containingvinyl monomer and an amide-group-containing vinyl monomer.

Further, in the above curable liquid resin composition providedaccording to the present invention, the vinyl monomer (a-2-1) is aperfluoroalkyl-group-containing vinyl monomer.

Further, in the above curable liquid resin composition providedaccording to the present invention, the (meth)acrylic liquid resin (A)contains 1 to 60% by weight of a functional vinyl monomer (a-2-2) havinga functional group which is inert to radical polymerization but isactive to radiation.

Further, in the above curable liquid resin composition providedaccording to the present invention, the functional vinyl monomer (a-2-2)is a vinyl monomer having an alicyclic epoxy group.

Further, in the above curable liquid resin composition providedaccording to the present invention, the functional vinyl monomer (a-2-2)is a siloxane-containing vinyl monomer having a siloxane bond.

Further, in the above curable liquid resin composition providedaccording to the present invention, the polymerizable vinyl monomer(a-2) is a monomer prepared by further incorporating the vinyl monomer(a-2-1) to the functional vinyl monomer (a-2-2), and the (meth)acrylicliquid resin (A) contains 0 to 79% by weight of the vinyl monomer(a-2-1).

Further, in the above curable liquid resin composition providedaccording to the present invention, the modified product of the liquidresin is a product obtained by reacting the (meth)acrylic liquid resin(A) having active hydrogen with a isocyanic ester compound (C) having anunsaturated double bond.

Further, in the above curable liquid resin composition providedaccording to the present invention, the (meth)acrylic monomer (B) has aviscosity of 0.01 to 100 poise (50° C.).

Further, in the above curable liquid resin composition providedaccording to the present invention, R¹ is the formula (1) is a hydrogenatom and/or R¹ in the formula (2) is a hydrogen atom.

Further, in the above curable liquid resin composition providedaccording to the present invention, the alkyl (meth)acrylate monomer(a-1-1) of the formula (1) has an average molecular weight of at least150.

Further, in the above curable liquid resin composition providedaccording to the present invention, the polyalkylene glyocl(meth)acrylate monomer (a-1-2) of the formula (2) has an averagemolecular weight of at least 220.

Further, in the above curable liquid resin composition providedaccording to the present invention, the composition has a viscosity of0.01 to 1,000 poise (50° C.).

Further, in the above curable liquid resin composition providedaccording to the present invention, the composition isradiation-curable.

Further, the present invention is directed to a curable printing inkcontaining the above liquid resin composition.

Further, the present invention is directed to a coating compositioncontaining the above liquid resin composition.

PREFERRED EMBODIMENTS OF THE INVENTION

In the present invention, the alkyl (meth)acrylate monomer (a1-1) of theformula (1) is used for bringing the (meth)acrylic resin into the stateof a liquid. Examples of the alkyl (meth)acrylate monomer of the formula(1) includes alkyl (meth)acrylates whose alkyl groups have 4 to 22carbon atoms, such as butyl (meth)acrylate, pentyl (meth)acrylate,heptyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,undecyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl(meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate,heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl(meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate anddocosyl (meth)acrylate. Acrylates having an alkyl group havingpreferably 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms,or methacrylates corresponding thereto, give a liquid resin having adesirable viscosity. When the number of carbon atoms is 3 or less, it isdifficult to obtain a liquid resin. When the number of carbon atoms is23 or more, undesirably, it is difficult to increase a polymerizationdegree, and crystallization proceeds, so that an obtained liquid resinhas a high viscosity and a special heating system is required forforming a film.

The average of the molecular weight of the alkyl (meth)acrylate monomerused in the present invention is at least 150, preferably in the rangeof from 160 to 350. When the average of the molecular weight is outsidethe above range, it is difficult to obtain a liquid resin having aviscosity in a desirable range.

In the present invention, the alkylene glycol (meth)acrylate monomer(a-1-2) is used for bringing the (meth)acrylic resin into the state of aliquid and for controlling the compatibility the liquid resin with othercomponents by changing the polarity of the liquid resin.

Examples of the alkylene glycol (meth)acrylate of the formula (2)include methoxytriethylene glycol (meth)acrylate, methoxytetraethyleneglycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate,propoxytetraethylene glycol (meth)acrylate, n-butoxytetraethylene glycol(meth)acrylate, n-pentoxytetraethylene glycol (meth)acrylate,tripropylene glycol (meth)acrylate, tetrapropylene glycol(meth)acrylate, methoxytripropylene glycol (meth)acrylate,methoxytetraropylenen glycol (meth)acrylate, ethoxytetrapropylene glycol(meth)acrylate, propoxytetrapropylene glycol (meth)acrylate,n-butoxytetrapropylene glycol (meth)acrylate, n-pentoxytetrapropyleneglycol (meth)acrylate, polytetramethylene glycol (meth)acrylate,methoxypolytetramethylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate,phenoxyytriethylene glycol (meth)acrylate, phenoxytetraethylene glycol(meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate,phenoxypolyethylene glycol (meth)acrylate, and phenoxytetrapropyleneglycol (meth)acrylate. Above all, when an acrylate having apolyoxyalkylene where m for repating units is 3 to 25, preferably 4 to22, or a methacrylate corresponding thereto, is used, the viscosity of acopolymer can be effectively decreased. Further, the use of the aboveacrylate or methacrylate is preferred since the crosslinking reaction ofa polyoxyalkylene side chain proceeds effectively when a composition iscured by irradiation with electron beam or γ ray. When m for therepeating units is 2 or less, it is difficult to obtain a liquid resin.When m is 26 or more, undesirably, it is difficult to increase apolymerization degree, and further, a resin is a solid at 50° C., sothat a special melting system is required for forming a film.

In the present invention, the average molecular weight of thepolyalkylene glycol (meth)acrylate monomer is at least 220, preferablyin the range of from 250 to 700. When the above average molecular weightis outside the above range, it is difficult to obtain a liquid resinhaving a viscosity in a desirable range.

The amount of the alkyl (meth)acrylic monomer (a-1-1) or thepolyalkylene glycol (meth)acrylate monomer (a-1-2) based on monomercomponents as components for the liquid resin (A) is 10 to 100% byweight, preferably 20 to 98% by weight, more preferably 40 to 95% byweight, further more preferably 40 to 90% by weight. When the aboveamount is smaller than the above lower limit, undesirably, a desirableviscosity can be no longer maintained.

Further, one of the (meth)acrylate monomers (a-1-1) and (a-1-2) may beused alone, while it is preferred to use both in combination in view ofa decrease in viscosity and an improvement in compatibility with othercomponents. The ratio of the (meth)acrylate monomers (a-1-1) and (a-1-2)by weight is 1:99˜95:5, more preferably 5:95˜90:50.

In the present invention, further, the vinyl monomer (a-2-1) having afunctional group inert to radiation and a functional vinyl monomer(a-2-2) having a functional group inert to radical polymerization butactive to radiation may be used as a polymerizable vinyl mnomer (a-2),for improving a cured coating film in water resistance and hardness solong as the liquid state of a resin can be maintained.

The vinyl monomer (a-2-1) includes alkyl (meth)acrylate whose alkylgroup has 3 carbon atoms or less, an alkylene glycol monomer of theformula (3), 11styrene, vinylbenzene, a carboxyl-group-containing vinylmonomer, a hydroxyl-group-containing vinyl monomer, anamide-group-containing vinyl monomer and aperfluoroalkyl-group-containing vinyl monomer. Of these, acarboxyl-group-containing vinyl monomer, a hydroxyl-group-containingvinyl monomer and an amide-group-containing vinyl monomer are preferredsince these vinyl monomers are excellent in the effect of imparting thecapability of adhesion to a substrate. A perfluoroalkyl-group-containingvinyl monomer is preferred since it improves a cured coating film inwater repellency and chemical resistance.

Specific examples of the above monomers are as follows.

Alkyl-group-possessing (meth)acrylates of which the alkyl has 3 carbonatoms or less, such as methyl methacrylate and ethyl methacrylate,

alkoxy-group-containing or phenoxy-group-containing alkylene glycol(meth)acrylate monomers such as methoxydiethylene glycol (meth)acrylate,methoxytriethylene glycol (meth)acrylate, phenoxydiethylene glycol(meth)acrylate and phenoxyethylene glycol (meth)acrylate,

aromatic vinyl monomers such as styrene and vinyltoluene,

carboxyl-group-containing vinyl monomers such as maleic acid, fumaricacid, itaconic acid, citraconic acid, alkyl or alkenyl monomesters ofthese, phthalic acid β-(meth)acryloxyethyl monoester, isophthalic acidβ-(meth)acryloxyethyl monoester, terephthalic acid β-(meth)acryloxyethylmonoester, succinic acid β-(meth)acryloxyethyl monoester, acrylic acid,methacrylic acid, crotonic acid and cinnamic acid,

hydroxyl-group-containing vinyl monomers such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, diethylene glycolmono(meth)acrylate and dipropylene glycol monomethacrylate,

amide-group-containing vinyl monomers, e.g., monoalkylol(meth)acrylamides such as (meth)acrylamide, N-methylol (meth)acrylamide,N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide,N-propoxymethyl-(meth)acrylamide, N-butoxymethyl-(meth)acrylamide andN-pentoxymethyl (meth)acrylamide, and dialkylol (meth)acrylamides suchas N,N-di(methylol)acrylamide, N-methylol-N-methoxymethyl(meth)acrylamide, N,N-di(methoxymethyl) acrylamide,N-ethoxymethyl-N-methoxymethyl methacrylamide, N,N-di(ethoxymethyl)acrylamide, N-ethoxymethyl-N-propoxymethyl methacrylamide,N,N-di(propoxymethyl) acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-di(butoxymethyl) acrylamide,N-butoxymethyl-N-(methoxymethyl) methacrylamide, N,N-di(pentoxymethyl)acrylamide and N-methoxymethyl-N-(pentoxymethyl) methacrylamide,

perfluoroalkylalkyl (meth)acrylates having a perfluoroalkyl group having1 to 20 carbon atoms, such as perfluoromethyl (meth)acrylate,perfluoroethylmethyl (meth)acrylate, 2-perfluorobutylethyl(meth)acrylate, 2-perfluorohexylethyl (meth)acrylate,2-perfluorooctylethyl (meth)acrylate, 2-perfluoroisononylethyl(meth)acrylate, 2-perfluorodecylethyl (meth)acrylate,perfluoropropylpropyl (meth)acrylate, perfluorooctylpropyl(meth)acrylate, perfluorooctylamyl (meth)acrylate andperfluorooctylundecyl (meth)acrylate, and

perfluoroalkyl-group-containing vinyl monomers, e.g.,perfluoroalkylalkyenes such as perfluorobutylethylene,perfluorohexylethylene, perfluorooctylethylene andperfluorodecylethylene.

A plurality of the above monomers may be used.

When the liquid resin is modified with an isocyanic ester compoundhaving an unsaturated double bond, the polymerizable vinyl monomer (a-2)for use in the liquid resin is selected from vinyl monomers containingactive hydrogen which is reactive with an isocyanate group, such ascarboxyl group, hydroxyl group or amide group. of these, a vinyl monomercontaining a hydroxyl group is preferred in view of reactivity with anisocyanate group and a low viscosity of the liquid resin.

In the present invention, the amount of the vinyl monomer (a-2-1) basedon the liquid resin which is a copolymer is 0 to 90% by weight,preferably 0 to 79% by weight, more preferably 1 to 50% by weight. Whenthe above amount is larger than the above upper limit, undesirably, theliquid resin has a high viscosity.

In the present invention, the functional vinyl monomer (a-2-2) having afunctional group which is inert to radical polymerization and its activeto radiation may be used as a polymerizable vinyl monomer (a-2), forimparting the liquid resin with the capability of crosslinking underradiation. The above functional vinyl monomer includes epoxy-containingvinyl monomers such as glycidyl (meth)acrylate having an epoxy group inits molecule and siloxane-containing vinyl monomers having a siloxanebond. of the epoxy-containing vinyl monomers, a vinyl monomer containingan alicyclic epoxy group is preferred since the liquid resin containingsuch a vinyl monomer has the high capability of crosslinking withelectron beam (EB).

In the present invention, an alicyclic-epoxy-group-containing vinylmonomer having an alicyclic epoxy group in its molecule is used as afunctional vinyl monomer (a-2-2), for promoting theradiation-crosslinkability of the (meth)acrylic liquid resin (A).

The above alicyclic-epoxy-group-containing vinyl monomer is notspecially limited so long as it is a compound having aradical-polymerizable vinyl group and an alicyclic epoxy group in itsmolecule. Above all, it is preferred to use any one of compounds of thefollowing formulae, since difficulties such as gelation, etc., do notmuch take place at the time of copolymerization with the alkyl(meth)acrylate monomer or at the time of removing a solvent. ##STR1##

In the above formulae, R¹ is a hydrogen atom or methyl, and Y is adivalent group of --{R⁴ COO}_(x) R⁵ -- in which R⁴ is a divalentaliphatic hydrocarbon group having 1 to 10 carbon atoms, R⁵ is adivalent hydrocarbon group having 1 to 6 carbon atoms and x is aninteger of 1 to 5.

Examples of the above alicyclic-epoxy-group-containing vinyl monomerinclude 3,4-epoxycyclohexylmethyl (meth)acrylate,1-vinyl-3,4-epoxycyclohexane and(3,4-epoxycyclohexyl-5-hydroxyhexanoiccarboxylate) (meth)acrylate.

The siloxane-containing vinyl monomer having a siloxane bond in itsmolecule, which is one monomer included in the functional vinyl monomer(a-2-2) used in the present invention, is used for promoting theradiation crosslinking capability of the (meth)acrylic liquid resin (A).

Examples of the above siloxane-containing vinyl monomer include(meth)acryloxyalkylalkoxysilanes such asγ-(meth)acryloxypropyltrimethoxysilane andγ-(meth)acryloxypropylmethyldimethoxysilane,(meth)acryloxyalkylalkoxyalkylsilane, trimethoxyvinylsilane,dimethoxyethylsilane, triethoxyvinylsilane, triethoxyallysilane,vinylmethyldimethoxysilane, vinylmethyldiethoxysilane andvinyltris(2-methoxyethoxy)silane.

In the present invention, the amount of the functional vinyl monomer(a-2-2) based on the liquid resin (A) is 1 to 60% by weight, preferably5 to 50% by weight. When the above amount is smaller than the abovelower limit, undesirably, a resin shows insufficient crosslinkingcapability, and a cured product is poor in solvent resistance. When theabove amount is larger than the above upper limit, undesirably, a resinhas a high viscosity in some cases or a solid resin is formed at roomtemperature, so that it is difficult to prepare a solventless liquidresin, and further, it is required to incorporate a large amount of acompound having a low molecular weight in order to prepare a compositionhaving a viscosity suitable for forming a film.

When the functional vinyl monomer (a-2-2) is used as a polymerizablevinyl monomer (a-2), the vinyl monomer (a-2-1) may be furtherincorporated. In this case, the amount of the vinyl monomer (a-2-1)based on the liquid resin (A) is 0 to 79% by weight, preferably 1 to 50%by weight.

However, when the alicyclic-epoxy-group-containing vinyl monomer is usedas a functional vinyl monomer (a-2-2), it is not desirable to use avinyl monomer (a-2-1) having a functional group, such as a carboxyl oramide group which is capable of reacting with an epoxy group. or, whenthe siloxane-containing vinyl monomer is used, it is not desirable touse a hydroxyl-group-containing vinyl monomer in combination. That isbecause these are liable to cause a gelation when the acrylic liquidresin is synthesized.

The average of molecular weights of the entire monomers used ascomponents for forming the (meth)acrylic liquid resin (A) is in therange of from 100 to 1,500, preferably 150 to 1,100. When the aboveaverage is outside the above range, undesirably, no liquid resin havinga viscosity in a desirable range can be obtained.

When the curable liquid resin composition of the present invention iscured by irradiation with electron beam, preferably, R¹ in each of theformulae (1), (2) and (3) is hydrogen. The other polymerizable vinylmonomer (a-2) that can be used in this case is preferably apolymerizable vinyl monomer which has no quaternary carbon in its mainchain when it is copolymerized, such as an acrylic monomer or styrene.

In the present invention, there may be used a liquid resin modifiedproduct obtained by reacting an isocyanate group of an isocyanic estercompound (C) having an unsaturated double bond with anactive-hydrogen-containing liquid resin prepared from anactive-11hydrogen-containing vinyl monomer (a-2-1) which is at least onemonomer selected from the above carboxyl-group-containing vinyl monomer,hydroxyl-group-containing vinyl monomer, amide-group-containing vinylmonomer or the like.

In the present invention, the isocyanic ester compound (C) refers to acompound having one isocyanate group and an unsaturated double bond inits molecule, and is used for modification for introducing aradiation-active crosslinking site to the liquid resin.

Examples of the above isocyanic ester compound (C) includemethacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate and(meth)acryloyl isocyanate.

Further, a compound obtained by reacting a diisocyanic ester compoundwith the above hydroxyl-group-, carboxyl-group- oramide-group-containing vinyl monomer in equimolar amounts can be alsoused as an isocyanic ester compound (C). The diisocyanic ester compoundincludes hexane 1,6-diisocyanate, isophorone diisocyanate,4,4'-diphenylmethane diisocyanate, polymeric diphenylmethanediisocyanate, xylylene duisocyanate, tolylene 2,4-diisocyanate,hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate,naphthylene diisocyanate, p-phenylene diisocyanate, tetramethylxylylenediisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylenediisocyanate, tolidine diisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate,m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanateand dimer acid diijocyanate.

In the present invention, the amount of the isocyanic ester compound (c)per mole of the vinyl monomer (a-2-1) used as a component for formingthe acrylic liquid resin is 0.1 to 100 mol, preferably 1 to 100 mol.

In the present invention, the modified product of the acrylic liquidresin with the isocyanic ester compound (C) is obtained by adding theisocyanic ester compound (C) to a synthesis solution during thesynthesis of the liquid resin. Otherwise, it can be also obtained byadding the isocyanic ester compound (C) to a mixture of the liquid resinwith the acrylic monomer (a). For the modification, a catalyst used forthe synthesis of usual urethane may be added, and the catalyst isselected from tin-containing catalysts such as tin octylate and tin2-ethylhexanoate. The amount of the catalyst is preferably 1 to 0.01% byweight based on the iscyanic ester compound (c).

When the curable liquid resin composition of the present invention iscured by irradiation with electron beam, preferably, R¹ in the formula(1) is hydrogen. The polymerizable vinyl monomer (a-2) that can be usedin this case is preferably a monomer having no quaternary carbon in itsmain chain, such as an acrylic monomer or styrene.

The (meth)acrylic liquid resin used in the present invention has anumber average molecular weight of 10,000 to 200,000, preferably 11,000to 100,000. When the above number average molecular weight is less thanthe above lower limit, undesirably, it is difficult to isolate a resincomponent from a polymerization solution in some cases, mechanicalproperties such as flexibility decrease, properties of a coating filmsuch as solvent resistanc and boiling water resistance decrease, and theodor of the monomer is intensified, since the content of a componenthaving a low molecular weight is large, and the odor of the monomer isintensified. Further, when the above number average molecular weight isgreater than the above upper limit, undesirably, it is required to add alarge amount of a compound having a low molecular weight in order toattain a viscosity at which the resin is capable of forming a film.

The acrylic liquid resin (A) used in the present invention can beprepared by a radical polymerization method in which a mixture of theabove monomers is dissolved in, or dropwise added to, a solvent in thepresence of a radical polymerization initiator. The radicalpolymerization initiator can be selected from known compounds, e.g.,peroxides such as benzoyl peroxide, t-butyl peroxide, cumenehydroxyperoxide, lauroyl peroxide, organic peroxides (described in Taisei-sha,"Handbook of Crosslinking Agents", pages 520-535, 2nd issue), azocompounds such as azobisisobutyronitrile and azobicyclohexanenitrile,and persulfate-containing initiators such as potassium persulfate andammonium persulfate. Above all, it is preferred to use an initiatorwhich is less capable of capturing hydrogen, since the polymerizationstably proceeds. In particular, when thealicyclic-epoxy-group-contalning vinyl monomer is used as a functionalvinyl monomer (a-2-2), it is preferred to use an initiator which is lesscapable of capturing hydrogen, such as an azo compound.

The above solvent includes ethyl acetate, toluene, methyl ethyl ketone,benzene, dioxane, n-propanol, methanol, isopropanol, tetrahydrofuran,n-butanol, sec-butanol, tert-butanol, isobutanol, methyl cellosolve,butyl cellosolve, methyl carbitol, ethyl carbitol, methyl cellosolveacetate, ethyl cellosolve acetate and diacetone alcohol.

In the present invention, the solvent used for the synthesis is removedby a method of precipitation purification or distillation after thesynthesis, whereby the liquid resin is formed. The viscosity of theobtained liquid resin or the modified product thereof, measured at 50°C., is 1 to 10,000 poise, preferably 5 to 10,000 poise, more preferably8 to 1,000 poise. When the viscosity of the liquid resin is lower thanthe above lower limit, undesirably, a repelling is caused when acomposition is coated to form a film or an infiltrating is caused at thetime of coating a paper sheet or printing. When the above viscosity ishigher than the above upper limit, undesirably, it is required to add alarge amount of the acrylic monomer (B) in order to decrease theviscosity.

In the present invention, the (meth)acrylic monomer (B) having at leastone unsaturated double bond in its molecule and having a number averagemolecular weight of 1,000 or less is used for adjusting the viscosityand the curability of the solventless liquid resin composition.

Examples of the above (meth)acrylia monomer (B) include monofunctional(meth)acrylic monomerB such as methyl (meth)acrylate, butyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, phenoxyethyl(meth)acrylate, phenoxymethyl (meth)acrylate, benzyl (meth)acrylate,isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate and(dicyclopentenyl)oxy (meth)acrylate, difunctional (meth)acrylic monomerssuch as ethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, tripropylene glycol di(meth)acrylate,polypropylene glycol di(meth)acrylate, 1,3-butylene glycoldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate,2-methyl-1,8-octanediol diacrylate, 1,9-nonanediol di(meth)acrylate,neopentyl glycol di(meth)acrylate,2,2-bis[4-{(meth)acryloxy-diethoxy}phenyl]propane,2,2-bis[4-{(meth)acryloxyethoxy}phenyl]propane,2,2-bis[4-{(meth)acryloxy-polyethoxy}phenyl]propane,2,2-bis[4-{(meth)acryloxy-dipropoxy}phenyl]propane,2,2-bis[4-{(meth)acryloxypropoxy}phenyl]propane,2,2-bis[4-{(meth)acryloxy-polypropoxy}phenyl]propane andtricyclo[5.2.1.0².6 ]decanyl di(meth)acrylate, and trifunctional orhigher (meth)acrylic monomers such as trimethylolpropanetri(meth)acrylate, tetramethylolmethane tri(meth)acrylate,tetramethylolethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylateand dipentaerythritol hexa(meth)acrylate.

The viscosity of the above (meth)acrylic monomer (B) is 0.01 to 60 poise(50° C.), preferably 0.1 to 50 poise (50° C.) or 0.01 to 100 poise (30°C.). The (meth)acrylic monomer having a viscosity lower than the abovelower limit has a large content having a low molecular weight, andundesirably, it has a high skin irritation value and a high volatility.The (meth)acrylic monomer having a viscosity higher than the above upperlimit is ndesirable, since it has a poor function as a viscosityadjusting agent.

In the present invention, the amount ratio of the (meth)acrylic liquidresin (A) and the (meth)acrylic monomer (B) is as follows. The amount ofthe (meth)acrylic monomer (B) per 100 parts by weight of the(meth)acrylic liquid resin (A) is 1 to 1,000 parts by weight, preferably2 to 500 parts by weight. When the amount ratio of the (meth)acrylicmonomer (B) is larger than the above, undesirably, the characteristicproperties of the liquid resin do not work, and as a result, a volumeshrinkage at a curing time is intense, the adhesion to a substrate ispoor, and a cured product is fragile. When the above amount ratio issmaller than the above, undesirably, a composition is poor in curabilityand is inferior in solvent resistance.

The viscosity of the composition of the present invention is 0.01 to1,000 poise, preferably 0.1 to 500 poise (50° C.). The compositionhaving a viscosity higher than the above upper limit is undesirable dueto its poor workability.

In the present invention, generally, the curable liquid resincomposition can be obtained by mixing the (meth)acrylic liquid resin (A)and the (meth)acrylic monomer (B), while the acrylic monomer (B) may beadded to an acrylic liquid resin (A) polymerization solution before asolvent is removed, whereby the composition can be obtained concurrentlywith the removal of the solvent.

In the present invention, the curable liquid resin composition maycontain curing agent resins such as an amino resin and a phenolic resinin order to improve its film formability and curing properties. Further,for improving the performance of a coating, the curable liquid resincomposition may contain generally usable polymers such as a knownpolyamide resin, a cellulose derivative, a vinyl-containing resin, apolyolefin, a natural rubber derivative, an acrylic resin, an epoxyresin, a polyester and a polystyrene, reactive resin having anunsaturated group, such as a urethane acrylic resin, an epoxy acrylicresin, an alkyd resin, a rosin-modified alkyd resin and alinseed-oil-modified alkyd resin, and dry oils such as linseed oil, tungoil and soybean oil. The amount of these based on the curable liquidresin composition is preferably 40% by weight or less, more preferably20% by weight or less. Further, a solvent, a compatibilizer, asurfactant or a lubricant may be added as required. The amount of theseis 20% by weight or less, preferably 10% by weight or less.

The curable liquid resin composition of the present invention can beused as various printing inks and colored coating compositions byincorporating proper amounts of colorants made of dyestuffs or pigmentssuch as carbon black, titanium white, phthalocyanine, ano dyestuff andquinacridone, or inorganic fillers such as Si-containing fine particles,mica and calcium carbonate.

The curable liquid resin composition of the present invention maycontain a known photo-polymerization sensitizer and initiator for curingit by irradiation with radiation.

A composition for a film-forming material, containing the curable liquidresin composition of the present invention, can be applied to metalplates such as a steel plate and an aluminum plate or substrates such asa plastic film, paper, a plastic film laminated sheet, etc., by anyconventional method, e.g., an application method using a roll coater, aknife coater, or the like, or a printing method such as an offsetprinting method, a gravure printing method, a letterpress printingmethod, a silk screen printing method, or the like, whereby a film(coating) having a thickness of 0.1 to 500 μm is generally formed. Thefilm (coating) can be cured by heating it or by irradiating it withradiation such as electron beam, ultraviolet, visible light or infrared.

When the curable liquid resin composition of the present invention iscured by irradiation with electron beam, there is used an electron beamirradiation apparatus having an energy preferably in the range of from10 to 1,000 kev, more preferably 30 to 300 keV. The dose thereof ispreferably 0.1 to 100 Mrad, more preferably 0.5 to 20 Mrad. When theabove dose is less than the above lower limit, no sufficiently curedproduct is obtained. When it is greater than the above upper limit,undesirably, a coating or a substrate are heavily damaged.

In the present invention, "to form a film" means "to form a film orcoating of a resin on a substrate made of as paper, a metal, a plastic,a ceramic, or the like by a method such as a printing method, a coatingmethod or an application method." The film or coating of a resingenerally has a thickness of 0.1 to 500 μm.

EXAMPLES

The present invention will be explained more in detail with reference toExamples hereinafter, while the present invention shall not be limitedthereto. In Examples, "wt %" stands for "% by weight".

⊙ Methods of measurements of number average molecular weight andviscosity are as follows.

1) Number average molecular weight: A value as a styrene in a gelpermeation chromatography (Tosoh Corp., SC-8020) was used. Further, as amolecular weight distribution (Mw/Mn), a value obtained with the aboveapparatus was used.

2) Viscosity: A value at a shear rate of 1 to 10/sec. by a stationaryviscosity measurement method using a rheometer (RDS-II, RFS-II, suppliedby Rheometrics) was used.

⊙ Electron beam irradiation apparatus and irradiation conditions are asfollows.

1) Area beam type electron beam irradiation apparatus CuretronEBC-200-20-30 (Nissin Hligh Voltage)

Acceleration voltage: 200 kV

The dose was adjusted in the range of 0.5 to 8 Mrad on the basis of acurrent amount.

2) MIN-EB (supplied by AIT)

Electron beam accelerating rate: 60 keV

The dose was adjusted in the range of 0.5 to 8 Mrad on the basis of abelt conveyor speed.

⊙ Abbreviations for compounds used in Examples and Comparative Examplesstand for the following compounds.

1) Compounds used for the synthesis of acrylic liquid resins

(a-1-1)

BA: Butyl acrylate

LA: Lauryl acrylate

EHA: 2-Ethylhexyl acrylate

SA: Stearyl alcohol

(a-1-2)

MTGA: Methoxytriethylene glycol monoacrylate

AM40G: Methoxytetraethylene glycol monoacrylate

AM90G: Methoxypolyethylene glycol

(polymerization degree 9) monoacrylate

AMP60G: Phenoxyhexaethylene glycol monoacrylate

(a-2-1)

AMP20G: Phenoxydiethylene glycol monoacrylate

ST: Styrene

AA: Acrylic acid

GMA: Glycidyl methacrylate

4HBA: 4-Hydroxybutyl acrylate

HEA: 2-Hydroxyethyl acrylate

AAm: Acrylamide

F-1: 2-(Perfluorooctyl)octyl methacrylate

(a-2-2)

M-100: 3,4-Epoxycyclohexylmethyl methacrylate

Si-1: γ-Methacryloxypropyltrimethoxyoilane

2) Compounds used as (meth)acrylic monomer (B)

POA: Phenoxyethyl acrylate (Mn=192, η=0.10P)

BzA: Bezyl acrylate (Mn=162, η=0.03 P)

EGDA: Ethylene glycol diacrylate (Mn=170, η=0.06 P)

PEG9DA: Polyethylene glycol diacrylate (Mn=508, η=0.362 P)

NODA: 1,9-Nonanediol diacrylate (Mn=268, η=0.073 P)

TPGDA: Tripropylene glycol diacrylate (Mn=300, η=0.12 P)

BP4EA: 2,2-Bis[4-{acryloxypolyethoxy}phenyl]-propane (Mn=512, η=7.5 P)

BP4PA: 2,2-Bis[4-{acryloxypolypropoxy}phenyl]-propane (Mn=560, η=17P)

TMPTA: Trimethylolpropane triacrylate (Mn=296, η=0.95 P)

TMPT3EO: EO-modified trimethylolpropane triacrylate, "NK EsterA-TMPT-3EO" (Mn=428, η=0.5 P) supplied by Shin-Nakamura ChemicalIndustry Co., Ltd.

DPHA: Dipentaerythritol hexaacrylate (Mn=578, η=50 P)

3) Isocyanic ester compound (C) or compounds used as material therefor

MOI: Methacryloyloxyethyl isocyanate

TDI: Tolylene 2,4-diisocyanate

4HBA: 4-Hydroxybutyl acrylate

Examples 1-9

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compound(o) shown in Table 1 in an amount ratio shown inTable 1. Azobisisobutyronitrile (AIBN) was used as an initiator (1% byweight based on the total monomer amount), and the monomer(s) wasrefluxed in an ethyl acetate solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 6hours. Then, 0.1% by weight of ATBN was further added, and further, themixture was continuously heated and stirred for 2 hours. After thereaction, a fractionating column was set between the reactor and thecondenser, and the hot water bath temperature was increased to 95° C.The solvent was distilled off while the stirring was continued underatmospheric pressure. Further, the solvent was completely distilled offby reducing the pressure inside the reactor to 40 mmHg under the sametemperature condition, to give a viscous liquid resin. The so-obtainedresin was measured for a number average molecular weight (Mn), amolecular weight distribution (Mw/Mn) and a viscosity (50° C.), andTable 1 shows the results.

                  TABLE 1                                                         ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                          Composition    Mn       Viscosity                                    Example (weight ratio) (): Mw/Mn (50° C.)/P(poise)                   ______________________________________                                        1      LA             1.27E4 (3.79)                                                                             35.3                                          2 LA:AMP20 = 80:20 1.68E4 (3.79) 100.0                                        3 LA:ST = 90:10 1.20E4 (3.17) 230.2                                           4 EHA 1.69E4 (4.17) 122.0                                                     5 EHA:LA = 50:50 1.36E4 (3.24)  75.4                                          6 EHA:AMP20G = 80:20 1.58E4 (3.58) 348.6                                      7 EHA:ST = 95:5 1.25E4 (3.17) 753.6                                           8 LA:EHA:ST:AMP20G = 1.33E4 (3.98) 247.5                                       30:45:5:20                                                                   9 BA:EHA = 20:80 1.59E4 (2.97) 142.3                                        ______________________________________                                    

Examples 10-38

Curable resin compositions prepared from the acrylic liquid resins (A)obtained in Examples 1 to 9 and acrylic monomers (B) were applied ontoPET films with a 0.5-mil applicator, and irradiated with electron beamat 2 Mrad. Table 2 shows components of the curable liquid resincompositions, the curability of coatings obtained by irradiation withelectron beam and residual ratios determined on the basis of weightchanges found after a 50-times MEK rubbing test.

                  TABLE 2                                                         ______________________________________                                        Composition and curing properties of curable                                    liquid resin composition                                                                                            MEK                                         Rubbing                                                                    Curable resin  Curability (After 50                                           composition (Ex. No.) Viscosity ◯: Cured times)                   (A):(B) (10/s) Δ: Tacking Residual                                     Ex. (Weight ratio) [P] X: Not cured ratio (%)                               ______________________________________                                        10  Ex. 1:NODA = 2:8                                                                              0.15      ◯                                                                          95                                       11 Ex. 4:NODA = 2:8 0.32 ◯ 100                                    12 Ex. 4:(NODA:TMPTA) = 0.41 ◯ 100                                 2:(7:1)                                                                      13 Ex. 5:NODA = 2:8 0.29 ◯ 100                                    14 Ex. 9:NODA = 2:8 0.33 ◯  95                                    15 Ex. 2:NODA = 2:8 0.31 ◯ 100                                    16 Ex. 2:BP4EA = 2:8 12.59  ◯  95                                 17 Ex. 2:BP4PA = 2:8 24.23  ◯ 100                                 18 Ex. 2:BP4PA = 4:6 34.54  ◯  90                                 19 Ex. 2:(NODA:TMPTA) = 0.82 ◯  95                                 3:(6:1)                                                                      20 Ex. 6:NODA = 2:8 0.40 ◯ 100                                    21 Ex. 6:BP4EA = 2:8 16.16  ◯  95                                 22 Ex. 6:BP4PA = 2:8 31.09  ◯ 100                                 23 Ex. 6:BP4PA = 3:7 42.05  ◯  95                                 24 Ex. 6:EGDA = 2:8 0.34 ◯ 100                                    25 Ex. 6:TMPTA = 2:8 3.09 ◯ 100                                   26 Ex. 6:DPHA = 3:7 89.53  ◯ 100                                  27 Ex. 6:(BP4PA:POA) = 15.09  ◯  95                                2:(7:1)                                                                      28 Ex. 3:(BP4PA:POA) = 5.77 ◯  95                                  2:(7:1)                                                                      29 Ex. 3:(BP4EA:BzA) = 8.56 ◯  95                                  2:(7:1)                                                                      30 Ex. 3:BP4PA = 2:8 18.62  ◯ 100                                 31 Ex. 7:(PB4PA:POA) = 21.71  ◯  95                                2:(7:1)                                                                      32 Ex. 7:(PB4EA:BzA) 10.86  ◯  95                                  2:(7:1)                                                                      33 Ex. 7:BP4EA = 2:8 18.86  ◯ 100                                 34 Ex. 9:NODA = 2:8 0.33 ◯  95                                    35 Ex. 8:BP4EA = 2:8 15.09  ◯ 100                                 36 Ex. 8:BP4PA = 2:8 29.03  ◯ 100                                 37 Ex. 7:(PB4EA:DPHA) = 18.23  ◯ 100                               2:(7:1)                                                                      38 Ex. 7:(PB4PA:TMPTA) = 16.39  ◯ 100                              2:(6:2)                                                                    ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Examples 39-43

30 Parts by weight of titanium white was added to, and mixed with, 70parts by weight of each of the curable resin compositions obtained inExamples 12, 17, 22, 27 and 38, and each mixture was dispersed with asand mill to give white inks. These inks were applied onto coat papersheets with a 0.5-mil applicator, and each coating was irradiated up toa dose of 2 Mrad to give cured coatings having excellent gloss. Table 3shows the results of MEK rubbing test and bending test (in which a 1 mmφ metal test rod was used and angles and numbers of times before thecoatings were broken were measured: ⊙: 180 degrees, at least 5 times, ◯:180 degrees, 1 to 4 times, Δ: 90 to 130 degrees, X: <90 degrees) of theso-obtained coatings together with viscosity values of the inks at 30and 50° C.

                  TABLE 3                                                         ______________________________________                                        Viscosity values and curing properties of                                       electron-beam-curable inks                                                                      MEK rubbing                                               Curable resin                                                                             Viscosity [P]                                                                             (50 times)                                              composition (10/s) Residual Bending                                         Ex.  Example No.                                                                              30° C.                                                                         50° C.                                                                       ratio (%) test                                  ______________________________________                                        39   Example 12 17.2    12.2  100       ◯                           40 Example 17 152 126.8 100 ◯                                     41 Example 22 354 223.9 100 ⊙                                    42 Example 27 110 78.3  90 ⊙                                     43 Example 38 124 90.6 100 ⊙                                   ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Examples 44-60

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compounds shown in Table 4 in a mixing ratio shown in Table4. Azobisisobutyronitrile (AIBN) was used as an initiator (1% by weightbased on the total amount of charged monomers), and the monomers wererefluxed in an ethyl acetate solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 6hours. Then, 0.1% by weight of AIBN was further added, and further, themixture was continuously heated and stirred for 2 hours. After thereaction, a fractionating column was set between the reactor and thecondenser, and the hot water bath temperature was increased to 95° C.The solvent was distilled off while the stirring was continued underatmospheric pressures Further, the solvent was completely distilled offby reducing the pressure inside the reactor to 40 mmHg under the sametemperature condition, to give a viscous liquid resin. The so-obtainedresin was measured for a number average molecular weight (Mn), amolecular weight distribution (Mw/Mn) and a viscosity (50° C.), andTable 4 shows the results.

                  TABLE 4                                                         ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                                                     Viscosity                                  Composition Mn (50° C.)                                               Example (weight ratio) (): Mw/Mn [P (poise)]                                ______________________________________                                        44        LA:AA = 90:10 1.60E4 (3.1)                                                                               64                                         45 LA:AA = 60:40 1.62E4 (2.8) 500                                             46 LA:GMA = 90:10 1.43E4 (2.5)  42                                            47 LA:AAm = 90:10 1.91E4 (3.4)  50                                            48 LA:HEA = 80:20 1.53E4 (2.2)  94                                            49 LA:4HBA = 80:20 1.54E4 (2.2)  78                                           50 LA:MTGA = 40:60 1.80E4 (3.2)  70                                           51 LA:AMP20G:AA = 1.36E4 (2.3) 103                                             80:15:5                                                                      52 EHA:AA = 95:5 1.48E4 (2.6) 170                                             53 EHA:GMA = 90:10 1.38E4 (2.3) 168                                           54 EHA:AAm = 90:10 1.74E4 (3.5) 200                                           55 EHA:4HBA = 90:10 1.48E4 (2.5) 188                                          56 EHA:MTGA = 70:30 1.45E4 (2.8) 120                                          57 EHA:MTGA = 60:40 1.67E4 (3.4) 110                                          58 EHA:4HBA:ST = 1.29E4 (2.1) 400                                              80:15:5                                                                      59 EHA:AMP20G:AA = 1.68E4 (3.4) 600                                            80:15:5                                                                      60 ERA:MTGA:AA = 1.79E4 (3.9) 580                                              80:15:5                                                                    ______________________________________                                    

Examples 61-86

Curable resin compositions prepared from the acrylic liquid resins (A)obtained in Examples 44 to 60 and acrylic monomers (B) were applied ontoPET films with a 0.5-mil applicator, and irradiated with electron beamat 2 Mrad. Table 5 shows components of the curable liquid resincompositions, the curability of coatings obtained by irradiation withelectron beam and residual ratios determined on the basis of weightchanges found after a 50-times MEK rubbing test.

                  TABLE 5                                                         ______________________________________                                        Composition and curing properties of curable                                    liquid resin composition                                                                                            MEK                                         Rubbing                                                                    Curable resin  Curability (After 50                                           composition (Ex. No.) Viscosity ◯: Cured times)                  Ex. (A):(B) (10/s) Δ: Tacking Residual                                  No. (Weight ratio) [P] X: Not cured ratio (%)                               ______________________________________                                        61   Ex. 44:NODA = 2:8                                                                             0.27     ◯                                                                          95                                       62 Ex. 45:NODA = 2:8 0.43 ◯ 100                                   63 Ex. 46:NODA = 2:8 0.26 ◯ 100                                   64 Ex. 47:NODA = 2:8 0.27 ◯  95                                   65 Ex. 48:NODA = 2:8 0.31 ◯  95                                   66 Ex. 49:NODA = 2:8 0.29 ◯ 100                                   67 Ex. 50:NODA = 2:8 0.29 ◯ 100                                   68 Ex. 51:NODA = 2:8 0.30 ◯ 100                                   69 Ex. 50:BP4PA = 2:8 22.56 ◯  95                                 70 Ex. 50:BP4PA = 4:6 29.94 ◯  90                                 71 Ex. 50:(BP4PA:TMPTA) = 12.60 ◯  95                              4:(3:3)                                                                      72 Ex. 50:TMPTA = 4:6 5.30 ◯ 100                                  73 Ex. 52:NODA = 2:8 0.34 ◯ 100                                   74 Ex. 53:NODA = 2:8 0.34 ◯  95                                   75 Ex. 54:NODA = 2:8 0.36 ◯ 100                                   76 Ex. 55:NODA = 2:8 0.35 ◯ 100                                   77 Ex. 56:BP4PA = 4:6 37.15 ◯  90                                 78 Ex. 56:(BP4PA:TMPTA) = 15.63 ◯  95                              4:(3:3)                                                                      79 Ex. 56:TMPTA = 4:6 6.58 ◯  95                                  80 Ex. 57:BP4EA = 2:8 12.83 ◯ 100                                 81 Ex. 57:(BP4EA:DPHA) = 38.79 ◯ 100                               4:(3:3)                                                                      82 Ex. 57:(DP4EA:DPHA) = 32.09 ◯  95                               4:(4:2)                                                                      83 Ex. 57:(PEG9DA:DPHA) = 17.86 ◯ 100                              4:(2:4)                                                                      84 Ex. 58:(BP4PA:BzA) = 16.96 ◯  95                                2:(7:1)                                                                      85 Ex. 59:(DP4PA:POA) = 20.75 ◯  95                                2:(7:1)                                                                      86 Ex. 60:(NODA:TMPTA) = 1.21 ◯ 100                                2:(4:4)                                                                    ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Example 87-91

30 Parts by weight of titanium white was added to, and mixed with, 70parts by weight of each of the curable resin compositions obtained inExamples 69, 71, 80, 83 and 85, and each mixture was dispersed with asand mill to give white inks. These inks were applied onto coat papersheets with a 1.0-mil applicator, and each coating was irradiated up toa dose of 2 Mrad to give cured coatings having excellent gloss. Table 6shows the results of MEK rubbing test and bending test (in which a 1 mmφ metal test rod was used and angles and numbers of times before thecoatings were broken were measured: ⊙: 180 degrees, at least 5 times, ∘:180 degrees, 1 to 4 times, Δ: 90 to 180 degrees, X: <90 degrees) of theso-obtained coatings together with viscosity values of the inks at 30and 50° C.

                  TABLE 6                                                         ______________________________________                                        Viscosity values and curing properties of                                       electron-beam-curable inks                                                                      MEK rubbing                                               Curable resin                                                                             Viscosity [P]                                                                             (50 times)                                              composition (10/s) Residual Bending                                         Ex.  Example No.                                                                              30° C.                                                                         50° C.                                                                       ratio (%) test                                  ______________________________________                                        87   Example 69 407.2   12.2   95       ⊙                          88 Example 71 360.0 126.8 100 ⊙                                  89 Example 80 350.3 223.9 100 ◯                                   90 Example 83 420.2 78.3 100 ◯                                    91 Example 85 500.7 90.6 100 ⊙                                 ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Examples 92-105

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compounds shown in Table 7 in a mixing ratio shown in Table7. Azobisisobutyronitrile (AIBN) was used as an initiator (1% by weightbased on the total amount of charged monomers), and the monomers wererefluxed in an isopropanol solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 6hours. Then, 0.1% by weight of AIBN was further added, and further, themixture was continuously heated and stirred for 2 hours. After thereaction, a fractionating column was set between the reactor and thecondenser, and the hot water bath temperature was increased to 95° C.The solvent was distilled off while the stirring was continued underatmospheric pressure. Further, the solvent was completely distilled offby reducing the pressure inside the reactor to 40 mmHg under the sametemperature condition, to give a viscous liquid resin. The so-obtainedresin was measured for a number average molecular weight (Mn), amolecular weight distribution (Mw/Mn) and a viscosity (50° C.), andTable 7 shows the results.

                  TABLE 7                                                         ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                                                    Viscosity                                     (50° C.)                                                            Exam- Composition Mn [P(poise)]                                               ple (weight ratio) (): Mw/Mn (10/s)                                         ______________________________________                                         92    AMP-60G:AA = 95.5                                                                             2.04E4 (5.2)                                                                              7,430                                         93 AMP-60G:AA = 90:10 2.45E4 (4.9) 9,360                                      94 AMP-60G:4HBA = 80:20 2.21E4 (5.6) 6,730                                    95 AMP-60G:GMA = 80:20 1.67E4 (4.4) 3,890                                     96 AMP-60G:AAm = 95:5 2.01E4 (3.1) 8,860                                      97 AMP-60G:AA:EHA = 1.89E4 (2.6) 8,030                                        80:5:15                                                                       98 AMP-60G:AA:ST = 1.77E4 (3.4) 9,060                                         90:5:5                                                                        99 AMP-60G:4HBA:EHA = 2.03E4 (2.9) 7,270                                      70:20:10                                                                     100 AMP-60G:GMA:EHA = 1.69E4 (2.6) 4,120                                       70:20:10                                                                     101 AM90G:AA = 95:5 1.95E4 (2.9) 211                                          102 AM90G:4HBA = 80:20 1.88E4 (3.1) 132                                       103 AM40G:AA = 95:5 1.53E4 (2.0) 189                                          104 AM40G:4HBA = 80:20 1.64E4 (2.0) 108                                       105 AM40G:4HBA:ST = 1.61E4 (2.2) 163                                           75:20:5                                                                    ______________________________________                                    

Examples 106-130

Curable resin compositions prepared from the acrylic liquid resins (A)obtained in Examples 92 to 105 and acrylic monomers (B) were appliedonto PET films with a 0.5-mil applicator, and irradiated with electronbeam at 2 Mrad. Table 8 shows components of the curable liquid resincompositions, the curability of coatings obtained by irradiation withelectron beam and residual ratios determined on the basis of weightchanges found after a 50-times MEK rubbing test.

                  TABLE 8                                                         ______________________________________                                        Composition and curing properties of curable                                    liquid resin composition                                                                                            MEK                                         Rubbing                                                                    Curable resin Vis- Curability (After 50                                       composition (Ex. No.) cosity ◯: Cured times)                     Ex. (A):(B) (10/s) Δ: Tacking Residual                                  No. (Weight ratio) [P] X: Not cured ratio (%)                               ______________________________________                                        106  Ex. 92:BP4PA = 2:8                                                                              49     ◯                                                                         100                                       107 Ex. 93:BP4PA = 2:8 51 ◯ 100                                   108 Ex. 94:BP4PA = 2:8 48 ◯ 100                                   109 Ex. 95:BP4PA = 2:8 43 ◯ 100                                   110 Ex. 96:BP4PA = 2:8 51 ◯ 100                                   111 Ex. 97:BP4PA = 2:8 50 ◯ 95                                    112 Ex. 98:BP4PA = 2:8 51 ◯ 100                                   113 Ex. 99:BP4PA = 2:8 49 ◯ 95                                    114 Ex. 100:BP4PA = 2:8 44 ◯ 95                                   115 Ex. 97:(BP4PA:TMPT3E0) = 25 ◯ 95                               2:(6:2)                                                                      116 Ex. 101:PEG9DA = 2:8 1.1 ◯ 95                                 117 Ex. 102:PEG9DA = 2:8 0.96 ◯ 95                                118 Ex. 101:(PEG9DA:TMPT3E0) = 1.2 ◯ 100                           2:(6:2)                                                                      119 Ex. 103:BP4PA = 2:8 24 ◯ 100                                  120 Ex. 104:BP4PA = 2:8 21 ◯ 100                                  121 Ex. 105:BP4PA = 2:8 23 ◯ 100                                  122 Ex. 103:BP4PA = 4:6 40 ◯ 95                                   123 Ex. 103:NODA = 2:8 0.29 ◯ 95                                  124 Ex. 103:PEG9DA = 2:8 0.11 ◯ 100                               125 Ex. 103:PEG14DA = 2:8 1.9 ◯ 90                                126 Ex. 103:IBXA = 2:8 0.38 ◯ 100                                 127 Ex. 103:(BP4PA:POA) = 8.4 ◯ 95                                 2:(6:2)                                                                      128 Ex. 103:(BP4PA:TMPT3EO) = 12 ◯ 100                             2:(6:2)                                                                      129 Ex. 103:(BP4PA:TMPT3EO) = 20 ◯ 100                             4:(4:2)                                                                      130 Ex. 103:(NODA:DPHA) = 1.1 ◯ 100                                2:(6:2)                                                                    ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Examples 131-135

30 Parts by weight of titanium white was added to, and mixed with, 70parts by weight of each of the curable resin compositions obtained inExamples 115, 118, 124, 126 and 130, and each mixture was dispersed witha sand mill to give white inks. These inks were applied onto coat papersheets with a 1.0-mil applicator, and each coating was irradiated up toa dose of 2 Mrad to give cured coatings having excellent gloss. Table 9shows the results of MEK rubbing test and bending test (in which a 1 mmφ metal test rod was used and angles and numbers of times before thecoatings were broken were measured: ⊙: 180 degrees, at least 5 times, ◯:180 degrees, 1 to 4 times, Δ: 90 to 180 degrees, X: <90 degrees) of theso-obtained coatings together with viscosity values of the inks at 30and 50° C.

                  TABLE 9                                                         ______________________________________                                        Viscosity values and curing properties of                                       electron-beam-curable inks                                                                      MEK rubbing                                               Curable resin                                                                             Viscosity [P]                                                                             (50 times)                                              composition (10/s) Residual Bending                                         Ex.  Example No.                                                                              30° C.                                                                         50° C.                                                                       ratio (%) test                                  ______________________________________                                        131  Example 115                                                                              450     86     95       ⊙                          132 Example 118 37 8.3 100 ⊙                                     133 Example 124 3.1 0.73 100 ⊙                                   134 Example 126 8.7 1.9 100 ◯                                     135 Example 130 26 6.4 100 ⊙                                   ______________________________________                                         Note:                                                                         Ex. = Example                                                            

Examples 136-145

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compounds shown in Table 10 in a mixing ratio shown inTable 10. Azobisisobutyronitrile (AIBN) was used as an initiator (1% byweight based on the total amount of charged monomers), and the monomerswere refluxed in an ethyl acetate solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 6hours. Then, 0.1% by weight of AIBN was further added, and further, themixture was continuously heated and stirred for 2 hours. After thereaction, a fractionating column was set between the reactor and thecondenser. The solvent was distilled off at a hot water bath temperatureof 85° C. while the stirring was continued under atmospheric pressure.Further, the solvent was completely distilled off by reducing thepressure inside the reactor to 40 mmHg at 60° C., to give a viscousliquid resin. The so-obtained resin was measured for a number averagemolecular weight (Mn), a molecular weight distribution (Mw/Mn) and aviscosity (50° C.), and Table 10 shows the results.

                  TABLE 10                                                        ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                                                  Vis-                                         Exam- Composition Mn cosity (50° C.)                                   ple (weight ratio) (): Mw/Mn [P (poise)]                                    ______________________________________                                        136   LA:EHA:M-100 = 50:10:40                                                                       1.20E4 (3.1)                                                                             3,563                                          137 EHA:M-100 = 60:40 1.02E4 (3.8) 4,830                                      138 LA:M-100 = 60:40 1.31E4 (2.5) 2,552                                       139 LA:EHA:M-100 = 40:40:20 1.51E4 (3.4) 700                                  140 LA:EHA:M-100 = 60:20:20 1.53E4 (2.2) 790                                  141 SA:M-100 = 80:20 1.12E4 (4.5) 847                                         142 LA:M-100 = 80:20 1.30E4 (4.6) 605                                         143 EHA:M-100 = 80:20 1.80E4 (3.2) 2,606                                      144 LA:AMP-20G:M-100 = 1.18E4 (3.4) 824                                        60:20:20                                                                     145 LA:ST:M-100 = 70:10:20 1.29E4 (3.9) 960                                 ______________________________________                                    

Examples 146-165

Radiation-curable liquid resin compositions prepared from the acrylicliquid resins (A) obtained in Examples 136 to 145 and acrylic monomers(B) were applied onto PET films with a 0.5-mil applicator, and theresultant coatings were irradiated with electron beam up to a dose of 2Mrad. Table 11 shows components of the curable liquid resincompositions, the curability and flexibility of films obtained byirradiation with electron beam and residual ratios determined on thebasis of weight changes found after a 50-times MEK rubbing test.

                                      TABLE 11                                    __________________________________________________________________________    Composition and curing properties of curable                                    liquid resin composition                                                                                  MEK                                                   Rubbing                                                                    Radiation-curable  Curability (After 50                                       resin composition Viscosity ◯: Cured times)                      Ex. (A(Ex. No.)):(B) (10/s) Δ: Tacking Residual                         No. (Weight ratio) [P] X: Not cured ratio (%) FTY*                          __________________________________________________________________________    146 Ex. 136:NODA = 2:8                                                                         1.58  ◯                                                                        100   ⊙                              147 Ex. 137:NODA = 2:8 0.67 ◯ 100 ◯                   148 Ex. 138:NODA = 2:8 0.59 ◯ 100 ⊙                  149 Ex. 139:NODA = 2:8 0.48 ◯ 100 ◯                   150 Ex. 140:NODA = 2:8 0.48 ◯ 95 ◯                    151 Ex. 141:NODA = 2:8 0.47 ◯ 95 ◯                    152 Ex. 142:NODA = 2:8 0.44 ◯ 95 ⊙                   153 Ex. 143:NODA = 2:8 1.68 ◯ 100 ⊙                  154 Ex. 144:NODA = 2:8 0.47 ◯ 100 ◯                   155 Ex. 145:NODA = 2:8 0.49 ◯ 100 ◯                   156 Ex. 137:NODA:TMPT3EO = 1.01 ◯ 100 ◯                                                   2:(6:2)                                   157 Ex. 139:NODA:TMPT3EO = 0.68 ◯ 100 ◯                                                   2:(6:2)                                   158 Ex. 139:NODA:TMPT3EO = 4.28 ◯ 95 ◯                 4:(4:2)                                                                      159 Ex. 141:NODA:TMPT3EO = 0.66 ◯ 100 ◯                                                   2:(6:2)                                   160 Ex. 144:NODA:TMPT3EO = 0.71 ◯ 100 ◯                                                   2:(6:2)                                   161 Ex. 137:BP4PA = 2:8 35.79 ◯ 95 ⊙                 162 Ex. 139:BP4PA = 4:6 24.32 ◯ 90 ⊙                 163 Ex. 139:BP4PA:TMPT3EO = 13.48 ◯ 100 ⊙                                                2:(6:2)                                   164 Ex. 139:BP4PA:TPGDA = 4.07 ◯ 100 ◯                 2:(4:4)                                                                      165 Ex. 144BP4PA:POA = 0.91 ◯ 95 ◯                     2:(6:2)                                                                    __________________________________________________________________________     Notes:                                                                        Ex. = Example,                                                                FTY* = Flexibility                                                            Flexibility test: A 1 mm .O slashed. 2metal test rod was used and angles      and numbers of times before the coatings were broken were measured:           ⊙: 180 degrees, at least 5 times, ◯: 180 degrees     1 to 4 times, Δ: 90 to 180 degrees, X: <90 degrees                 

Examples 166-171

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compounds shown in Table 12 in a mixing ratio shown inTable 12. Azobisisobutyronitrile (AIBN) was used as an initiator (1% byweight based on the total amount of charged monomers), and the monomerswere refluxed in an ethyl acetate solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 6hours. Then, 0.1% by weight of AIBN was further added, and further, themixture was continuously heated and stirred for 2 hours. After thereaction, a fractionating column was set between the reactor and thecondenser, and the solvent was distilled off while the stirring wascontinued at a hot water bath temperature of 85° C. under atmosphericpressure. Further, the solvent was completely distilled off by reducingthe pressure inside the reactor to 40 mmHg at 60° C., to give a viscousliquid resin. The so-obtained resin was measured for a number averagemolecular weight (Mn), a molecular weight distribution (Mw/Mn) and aviscosity (50° C.), and Table 12 shows the results.

                  TABLE 12                                                        ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                                                     Viscosity                                  Composition Mn (50° C.)                                               Example (weight ratio) ( ):Mw/Mn [P (poise)]                                ______________________________________                                        166    AM40G:M-100 = 80:20                                                                              2.26 E4 (4.1)                                                                             956                                       167 AM40G:M-100 = 70:30 3.60 E4 (4.8) 1,676                                   168 AM90G:M-100 = 80:20 1.75 E4 (3.6)   583                                   169 AMP60G:M-100 = 80:20 2.64 E4 (4.5)   745                                  170 AM90G:EHA:M-100 = 30:30:40 3.67 E4 (2.9) 1,580                            171 AM90G:EHA:M-100 = 40:40:20 1.91 E4 (3.4) 1,080                          ______________________________________                                    

Examples 172-183

Radiation-curable liquid resin compositions prepared from the acrylicliquid resins (A) obtained in Examples 166 to 171 and acrylic monomers(B) were applied onto PET films with a 0.5-mil applicator, and theresultant coatings were irradiated with electron beam under variousconditions. Table 13 shows components of the curable liquid resincompositions, the curability and flexibility of films obtained byirradiation with electron beam and residual ratios determined on thebasis of weight changes found after a 50-times MEK rubbing test.

                                      TABLE 13                                    __________________________________________________________________________    Composition and curing properties of curable                                    liquid resin composition                                                                                  MEK                                                   Rubbing                                                                    Curable resin  Curability (After 50                                           composition Viscosity ◯: Cured times)                            Ex. (A(Ex. No.)):(B) (10/s) Δ: Tacking Residual                         No. (Weight ratio) [P] X: Not cured ratio (%) FTY*                          __________________________________________________________________________    172 Ex. 166:TPGDA = 2:8                                                                        4.36  ◯                                                                        100   ◯                               173 Ex. 167:TPGDA = 4:6 5.46 ◯ 100 ◯                  174 Ex. 168:TPGDA = 4:6 6.94 ◯ 100 ⊙                 175 Ex. 169:TPGDA = 4:6 7.66 ◯ 100 ⊙                 176 Ex. 170:NODA = 4:6 3.96 ◯ 100 ◯                   177 Ex. 170:NODA = 6:4 29.14 ◯ 100 ⊙                 178 Ex. 171:NODA = 4:6 3.40 ◯ 95 ◯                    179 Ex. 171:(NODA:TMPTA) = 25.62 ◯ 100 ◯                                                  6:(2:2)                                   180 Ex. 166:BP4PA = 2:8 25.88 ◯ 100 ⊙                181 Ex. 168:BP4PA = 2:8 23.45 ◯ 100 ⊙                182 Ex. 170:(BP4PA:TPGDA) = 13.04 ◯ 100 ◯                                                 4:(2:4)                                   183 Ex. 171:(BP4PA:TPGDA) = 11.20 ◯ 100 ⊙                                                4:(2:4)                                 __________________________________________________________________________     Notes:                                                                        Ex. = Example,                                                                FTY* = Flexibility                                                       

Examples 184-190

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with compounds shown in Table 14 in a mixing ratio shown inTable 14. Azobisisobutyronitrile (AIBN) was used as an initiator (1% byweight based on the total amount of charged monomers), and the monomerswere refluxed in an ethyl acetate solvent (monomer concentration at thecharging time: 33% by weight) in a hot water bath set at 85° C. for 5hours. After the reaction, a fractionating column was set between thereactor and the condenser, and the solvent was distilled off while thestirring was continued with heating with a mantle heater underatmospheric pressure. Further, the solvent was completely distilled offby reducing the pressure inside the reactor to 40 mmHg at 100° C., togive a viscous liquid resin. The so-obtained resin was measured for anumber average molecular weight (Mn), a molecular weight distribution(Mw/Mn) and a viscosity (50° C.), and Table 14 shows the results.

                  TABLE 14                                                        ______________________________________                                        Composition of (meth)acrylic liquid resin and                                   results of measurement of physical properties                                                                     Viscosity                                  Composition Mn (50° C.)                                               Example (weight ratio) ( ):Mw/Mn [P (poise)]                                ______________________________________                                        184    EHA:Si-1 = 80:20  2.26 E4 (4.1)                                                                            220                                         185 EHA:AM90G:Si-1 = 60:20:10 3.60 E4 (4.8) 82                                186 LA:Si-1 = 60:40 1.75 E4 (3.6) 53                                          187 EHA:F-1:M-100 = 80:5:15 1.64 E4 (4.5) 435                                 186 AM90G:EHA:F-1 = 40:55:5 1.67 E4 (2.9) 97                                  189 AM90G:EHA:AA = 40:55:5 1.91 E4 (3.4) 122                                ______________________________________                                    

Examples 190-200

Radiation-curable liquid resin compositions prepared from the acrylicliquid resins (A) obtained in Examples 184 to 189 and acrylic monomers(B) were applied onto art paper sheets with a #8 bar coater, and a PETfilm having a thickness of 75 μm was cast thereon each. The resultantcoatings were irradiated with electron beam up to a dose of 2 MRad onthe coatings of the compositions. After the irradiation, the PET filmswere peeled off, to give coated paper sheets which were free of acurling caused by curing-induced shrinkage and were excellent in glossand solvent resistance. The coated paper sheets for which the resinsobtained in Examples 184 to 186 were applied further heated in an ovenat 80° C. for overnight (12 hours) to show improved solvent resistance.Table 15 shows components and viscosity values of the curable liquidresin compositions, and evaluation results of the curability of thecoated paper sheets obtained by irradiation with electron beam, theadhesion thereof to a substrate (film non-peeling ratio by a Cellophanetape peeling test), the curling resistance thereof and the solventresistance thereof (residual ratio determined on the basis of weightchanges found after a 50-times MEK rubbing test).

                  TABLE 15                                                        ______________________________________                                        Composition and curing properties of curable                                    liquid resin composition                                                    ______________________________________                                             Curable resin        Viscosity                                                                              Curability                                    composition (10/s) ◯: Cured                                      Ex. (A(Ex. No.)):(B) [P] Δ: Tacking                                     No. (Weight ratio) (50° C.) X: Not cured                             ______________________________________                                          190 184:TPGDA = 2:8 0.54 ◯                                        191 184:TMPT3EO = 2:8 1.69 ◯                                      192 184:BS550:TMPT3EO = 1:1:8 1.97 ◯                              193 185:NODA:TMPT3EO = 2:1:7 1.59 ◯                               194 186:TMPT3EO = 2:8 1.39 ◯                                      195 186:TMPT3EO = 4:6 3.23 ◯                                      196 167:TPGDA = 2:8 0.62 ◯                                        197 188:TPGDA = 2:8 0.45 ◯                                        198 187:189:TPGDA:TMPT3EO = 2:1:3:4 2.14 ◯                        199 188:189:TPGDA:TMPT3EO = 2:1:3:4 1.62 ◯                        200 189:TPGDA:TMPT3EO = 3:3:4 1.70 ◯                            ______________________________________                                               Adhesion               Solvent                                           Ex. to substrate Curling resistance [%]                                       No. [%] resistance A  B                                                     ______________________________________                                          190 100 ◯ 90 → 95                                          191 100 ◯ 95 → 100                                         192 100 Δ 95 → 95                                                193 100 ◯ 90 → 100                                         194 100 ◯ 95 → 100                                         195 100 ◯ 80 → 100                                         196 100 ◯ 100                                                     197 100 ◯ 100                                                     198 100 ◯ 100                                                     199 100 ◯ 100                                                     200 100 ◯  95                                                   ______________________________________                                         Notes:                                                                        Ex. = Example,                                                                Curling resistance: ◯ Flat, Δ State where a sheet was       curled to some extent.                                                        Solvent resistance: A = Solvent resistance after irradiation with electro     beam, B = Solvent resistance after standing at 80° C. for 12 hours     In Example 196 and thereafter, values of solvent resistance after             irradiation with electron beam are shown.                                

Example 201

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with 80 g of EHA and 20 g of 4HBA. Azobisisobutyronitrile (AIBN)was used as an initiator (1% by weight based on the total amount of thecharged monomers), and the monomers were refluxed in an ethyl acetatesolvent (monomer concentration at the charging time: 33% by weight) in ahot water bath set at 85° C. for 5 hours. After the reaction, afractionating column was set between the reactor and the condenser, andthe solvent was distilled off while the stirring was continued withheating with a mantle heater under atmospheric pressure. Further, thesolvent was completely distilled off by reducing the pressure inside thereactor to 40 MmHg at 100° C., to give a viscous liquid resin having amolecular weight, Mn, of 15,100 (MW/Mn=2.8) and a viscosity of 270 P(yield 98%). To 50 g of the obtained liquid resin was added 50 g ofTPGDA, and the mixture was stirred in a hot water bathset at 70° C. toform a uniform solution. Then, 10.2 g of MOI was dropwise added, and themixture was stirred for 30 min, 0.1022 g of tin 2-ethylhexanoate wasadded, and the mixture was continuously stirred at 70° C. until thecharacteristic peak of isocyanate at or around 2,300 cm⁻¹ of infrared(IR) spectrum disappeared. The resultant composition obtained from themodified product of the liquid resin and TPGDA had a viscosity of 10.4poise (50° C.).

Example 202

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with 60 g of EHA and 40 g of 4HBA. Azobisisobutyronitrile (AIBN)was used as an initiator (1% by weight based on the total amount of thecharged monomers), and the monomers were refluxed in an ethyl acetatesolvent (monomer concentration at the charging time: 33% by weight) in ahot water bath set at 85° C. for 5 hours. After the reaction, afractionating column was set between the reactor and the condenser, andthe solvent was distilled off while the stirring was continued withheating with a mantle heater under atmospheric pressure. Further, thesolvent was completely distilled off by reducing the pressure inside thereactor to 40 mmHg at 100° C., to give a viscous liquid resin having amolecular weight, Mn, of 14,800 (MW/Mn=3.5) and a viscosity of 589 P(yield 97%).

A 500-ml four-necked round-bottomed flask having a stirrer, anitrogen-introducing tube, a temperature sensor and a condenser wascharged with 20 g of 4HBA and 20 g of ethyl. acetate. A mixture solutioncontaining 24 g of TDI and 24 g of ethyl acetate was dropwise added witha dropping funnel. The resultant mixture was stirred in a hot water bathat 70° C. for about 30 minutes, and 0.24 g of tin 2-ethylhexanoate wasadded. The heating and stirring of the mixture was continued for 3hours, to give an isocyanic ester compound having an acrylic group. Tothis socyanic ester compound was added 50 g of the liquid resin obtainedby the above reaction, with stirring, and the mixture was stirred in ahot water bath at 60° C. for about 30 minutes until the mixture washomogeneous. Then, 0.24 g of tin 2-ethylhexanoate was added, and themixture was continuously stirred at 60° C. until the characteristicabsorption peak of isocyanate at or around 2,300 cm⁻¹ of infrared (IR)spectrum disappeared. After the reaction, a fractionating column was setbetween the reactor and the condenser, and the solvent was completelydistilled off by reducing the pressure inside the reactor to 10 mmHg orlower with heating at 40° C., to give a liquid resin modified producthaving a viscosity of 2,060 poise (50° C.).

Examples 203-205

Radiation-curable liquid resin compositions prepared from the acrylicliquid resins obtained in Examples 201 and 202 and acrylic monomers (B)were applied onto aluminum plates with a #8 bar coater, and theresultant coatings were irradiated with electron beam up to a dose of 4MRad. Table 16 shows components and viscosity values of the curableliquid resin compositions, and evaluation results of the curability(pencil hardness) of the coatings obtained by irradiation with electronbeam, the adhesion thereof to a substrate (film non-peeling ratio by aCellophane tape peeling test) and the solvent resistance thereof(residual ratio determined on the basis of weight changes found after a50-times MEK rubbing test).

                  TABLE 16                                                        ______________________________________                                        Composition and curing properties of curable                                    liquid resin composition                                                             Curable resin                                                           composition Viscosity  Adhesion                                               (Modified product) (10/s) Curability to                                      Ex. (Ex. No.)):(B) [P] Pencil substrate                                       No. (Weight ratio) (50° C.) hardness [%] SR*                         ______________________________________                                        203  201(modified  10.4     HB     100    100                                    product:TPGDA =                                                               1:1)                                                                         204 201:TMPT3EO = 4:1  5.7 H 100 100                                          205 202:TPGDA = 1:1 15.7 H 100 100                                            206 202:TMPT3EO = 1:1 32.1 2H  100 100                                      ______________________________________                                         SR = Solvent resistance                                                  

INDUSTRIAL UTILITY

The present invention provides a curable liquid resin composition whichis free from polluting a working environment in a coating step withcompounds having a low molecular weight and being dissipated, which doesnot release an organic solvent or compounds having a low molecularweight into atmosphere so that a film can be formed without requiring nospecial exhaust gas treatment equipment. Further, the present inventionprovides a curable liquid resin composition which can form a film by anapplication method using a roll coater, a knife coater, or the like, orby a printing method such as an offset printing method, a gravureprinting method, a letterpress printing method, or the like, and whichcan be cured by drying it under heat or by irradiating it with radiationsuch as electron beam, ultraviolet, visible light or infrared.

What is claimed is:
 1. A curable liquid resin composition containing 100parts by weight of the following (meth)acrylic liquid resin (A) and 1 to1,000 parts by weight of a (meth)acrylic monomer (B) having anunsaturated double bond in its molecule and having a number averagemolecular weight of 1,000 or less,the (meth)acrylic liquid resin (A)being a liquid resin which is obtained by polymerizing monomerscontaining 10 to 100% by weight of an alkyl (meth)acrylate monomer(a-1-1) of the formula (1),

    CH.sub.2 ═C(R.sup.1)COO--R.sup.2                       ( 1)

wherein R¹ is a hydrogen atom or CH₃ and R² is an alkyl group having 4to 22 carbon atoms, and/or an alkylene glycol (meth)acrylate monomer(a-1-2) of the formula (2),

    CH.sub.2 ═C(R.sup.1)COO (C.sub.n H.sub.2n O).sub.m R.sup.3( 2)

wherein R¹ is a hydrogen atom or CH₃, R³ is an alkyl group having 1 to 5carbon atoms or a phenyl group, n is an integer of 1 to 3, and m is aninteger of 3 to 25, and 0 to 90% by weight of other polymerizable vinylmonomer (a-2), an average of molecular weights of all the monomers being150 to 1,500, the liquid resin having a number average molecular weightof 10,000 to 200,000 and a viscosity of 1 to 10,000 poise (50° C.), orthe (meth)acrylic liquid resin (A) being a modified product of the aboveliquid resin.
 2. A curable liquid resin composition according to claim1, wherein the polymerizable vinyl monomer (a-2) is a vinyl monomer(a-2-1) having a functional group inert to radiation.
 3. A curableliquid resin composition according to claim 2, wherein the vinyl monomer(a-2-1) is a component for forming the (meth)acrylic liquid resin (A)and contained therein in an amount of 1 to 50% by weight.
 4. A curableliquid resin composition according to claim 2, wherein the vinyl monomer(a-2-1) is at least one monomer selected from the group consisting ofalkyl (meth)acrylate whose alkyl group has 3 carbon atoms or less, analkylene glycol (meth)acrylate monomer of the formula (3),

    CH.sub.2 ═C(R.sup.1)COO(C.sub.n H.sub.2n O).sub.m R.sup.3( 3)

wherein R¹ is a hydrogen atom or CH₃, R³ is an alkyl group having 1 to 5carbon atoms or a phenyl group, n is an integer of 1 to 4, and m is aninteger of 2 or less,styrene and vinyltoluene.
 5. A curable liquid resincomposition according to claim 2, wherein the vinyl monomer (a-2-1) isat least one monomer selected from the group consisting of acarboxyl-group-containing vinyl monomer, a hydroxyl-group-containingvinyl monomer and an amide-group-containing vinyl monomer.
 6. A curableliquid resin composition according to claim 2, wherein the vinyl monomer(a-2-1) is a perfluoroalkyl-group-containing vinyl monomer.
 7. A curableliquid resin composition according to claim 2, wherein the polymerizablevinyl monomer (a-2) is a functional vinyl monomer (a-2-2) having afunctional group which is inert to radical polymerization but is activeto radiation.
 8. A curable liquid resin composition according to claim7, wherein the functional vinyl monomer (a-2-2) is a component forforming the (meth)acrylic liquid resin (A) and contained therein in anamount of 1 to 60% by weight.
 9. A curable liquid resin compositionaccording to claim 7, wherein the functional vinyl monomer (a-2-2) is avinyl monomer having an alicyclic epoxy group.
 10. A curable liquidresin composition according to claim 7, wherein the functional vinylmonomer (a-2-2) is a siloxane-based vinyl monomer having a siloxanebond.
 11. A curable liquid resin composition according to claim 7,wherein the polymerizable vinyl monomer (a-2) is a monomer prepared byfurther incorporating the vinyl monomer (a-2-1) to the functional vinylmonomer (a-2-2).
 12. A curable liquid resin composition according toclaim 11, wherein the vinyl monomer (a-2-1) is a component for formingthe (meth)acrylic liquid resin (A) and contained therein in an amount of0 to 79% by weight.
 13. A curable liquid resin composition according toclaim 1, wherein the modified product of the liquid resin is a reactionproduct from the (meth)acrylic liquid resin (A) having active hydrogenand an isocyanic ester compound (C) having an unsaturated double bond.14. A curable liquid resin composition according to claim 13, whereinthe isocyanic ester compound (C) is used in an amount of 0.1 to 100 molper mole of the vinyl monomer (a-2-1).
 15. A curable liquid resincomposition according to claim 1, wherein the (meth)acrylic monomer (B)has a viscosity of 0.01 to 100 poise (measured at a temperature of 30°C.).
 16. A curable liquid resin composition according to claim 1,wherein the (meth)acrylic monomer (B) has a viscosity of 0.01 to 60poise (measured at a temperature of 30° C.).
 17. A curable liquid resincomposition according to claim 1, wherein the (meth)acrylic monomer (B)has a number average molecular weight of 1,000 or less.
 18. A curableliquid resin composition according to claim 1, wherein R¹ in the formula(1) is a hydrogen atom and/or R¹ in the formula (2) is a hydrogen atom.19. A curable liquid resin composition according to claim 1, wherein thealkyl (meth)acrylate monomer (a-1-1) of the formula (1) has an averagemolecular weight of at least
 150. 20. A curable liquid resin compositionaccording to claim 1, wherein the alkylene glycol (meth)acrylate monomer(a-1-2) of the formula (2) has an average molecular weight of at least220.
 21. A curable liquid resin composition according to claim 1,wherein the curable liquid resin composition has a viscosity of 0.01 to1,000 poise (measured at a temperature of 50° C.).
 22. A curable liquidresin composition according to claim 1, wherein the curable liquid resincomposition is radiation-curable.
 23. A curable printing ink containingthe curable liquid resin composition recited in claim
 22. 24. A coatingcomposition containing the curable liquid resin composition recited inclaim 22.